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1.
J Fish Biol ; 2024 Jan 16.
Artículo en Inglés | MEDLINE | ID: mdl-38226528

RESUMEN

Acoustic telemetry has seen a rapid increase in utility and sophistication in recent years and is now used extensively to assess the behavior and survival rates of many aquatic animals, including the Atlantic salmon. As part of the salmon's complex life cycle, salmon smolts are thought to make a unidirectional migration from fresh water to the sea, which is initiated by changes in their physiology. However, some tag movement patterns do not conform with this and can be difficult to explain, particularly if the tagged fish has been eaten by a predator. This study combines the use of predator tags with machine learning techniques to understand the fate of migrating salmon smolts and thereby improve estimates for migration success. Over 3 years between 2020 and 2022, 217 salmon smolts (including wild and hatchery-reared ranched fish) were acoustically tagged and released into an embayment on the west coast of Ireland. Some tagged smolts were observed to return from the estuary back into a saline lagoon through which they had already migrated. To distinguish between the movement of a salmon smolt and that of a predator, predator tags were deployed in migrating smolts in 2021 and 2022. The addition of a temperature sensor in 2022 enabled the determination of predator type causing the returning movement. A significant number of predator tags were triggered, and the patterns of movement associated with these triggered tags were then used with two types of machine learning algorithms (hierarchical cluster analysis and random forest) to identify and validate the behavior of smolts tagged without extra sensors. Both models produced the same outputs, grouping smolts tagged with predator tags with smolts tagged without the additional sensors but showing similar movements. A mammalian predator was identified as the cause of most reversal movement, and hatchery-reared ranched smolts were found to be more likely predated upon by this predator than wild smolts within the lake and the estuary. However, overall migration success estimates were similar for both wild and hatchery-reared ranched fish. This study highlights the value of predator tags as an essential tool in the overall validation of detection data.

2.
Rheumatol Int ; 39(10): 1759-1766, 2019 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-31482199

RESUMEN

Rheumatoid arthritis (RA) is associated with an increased risk of cardiovascular disease (CVD). Advanced measures of cardiorespiratory fitness (CRF) are associated with CVD risk factors. The present study aimed to examine whether CVD risk factors can predict clinic-based measures of CRF, using the Siconolfi step test and to determine if exercise can improve RA patients' cardiovascular health. Sixty-five RA patients (46 females, age 58 ± 11 years) completed assessments of CRF, CVD risk factors, body composition and RA characteristics. Ten patients participated in a follow-up 8-week exercise intervention. CRF was low (22 ml kg-1 min-1) and associated with higher diastolic blood pressure (r = - 0.37, p = 0.002), higher global CVD risk (r = - 0.267, p = 0.031) and worse body composition profile (body fat, r = - 0.48, p < 0.001; waist, r = - 0.65, p < 0.001; hip, r = - 0.58, p < 0.001). Regular exercise significantly improved CRF (p = 0.021), lower body strength (p < 0.001), agility (p < 0.001), systolic blood pressure (p = 0.021), body fat (p = 0.018), waist circumference (p = 0.035), hip circumference (p = 0.016), disease activity (p = 0.002), disability (p = 0.007) and QoL (p = 0.004). Elevated diastolic blood pressure and worse body composition profile are strong predictors of clinic-based measures of CRF. CRF is an important determinant of CVD risk and warrants inclusion in the routine assessment of RA patients. Regular exercise can improve CRF and CVD risk factors without any exacerbation of disease activity and should be offered as part of routine care.


Asunto(s)
Artritis Reumatoide/terapia , Capacidad Cardiovascular , Enfermedades Cardiovasculares/prevención & control , Terapia por Ejercicio , Anciano , Artritis Reumatoide/complicaciones , Artritis Reumatoide/diagnóstico , Artritis Reumatoide/fisiopatología , Presión Sanguínea , Composición Corporal , Enfermedades Cardiovasculares/diagnóstico , Enfermedades Cardiovasculares/etiología , Enfermedades Cardiovasculares/fisiopatología , Estudios Transversales , Tolerancia al Ejercicio , Femenino , Estado de Salud , Humanos , Estudios Longitudinales , Masculino , Persona de Mediana Edad , Fuerza Muscular , Calidad de Vida , Medición de Riesgo , Factores de Riesgo , Factores de Tiempo , Resultado del Tratamiento
3.
Ir J Med Sci ; 186(3): 767-771, 2017 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-28132158

RESUMEN

BACKGROUND: Spinal cord stimulation (SCS) is now established as the primary treatment for failed back surgery syndrome (FBSS). Commonly, patients with chronic pain and FBSS often report symptoms of anxiety and depression resulting from this condition. These factors can modulate and amplify the pain experience, therefore, further challenging treatment success. AIMS: This study examined the efficacy of SCS on alleviating the symptoms of anxiety and depression associated with chronic pain as well as pain intensity in a group of patients with FBSS. METHODS: A convenience sample (n = 26) was selected for participation. Questionnaires [Hospital Anxiety and Depression Scale (HADS) and Brief Pain Inventory Short Form (BPI-SF)] were completed and examined pre and post spinal cord implant. RESULTS: Analysis of the data 1 year following SCS indicates that there was a statistical significant improvement in the symptoms of depression and anxiety reported as well as pain intensity in all participants (p < 0.001). Both anxiety and depression scores on the HADS were significantly lower compared to baseline (p < 0.001). Pain intensity scores decreased by ≥50% from baseline in all participants. Opioid analgesia was discontinued by 90% (n = 8) of participants. CONCLUSION: Whilst it is already recognised that SCS reduces pain in FBSS, this study demonstrated that it also reduced the symptoms of anxiety and depression with an associated reduction in opioid consumption.


Asunto(s)
Ansiedad/etiología , Dolor Crónico/etiología , Depresión/etiología , Síndrome de Fracaso de la Cirugía Espinal Lumbar/complicaciones , Síndrome de Fracaso de la Cirugía Espinal Lumbar/psicología , Estimulación de la Médula Espinal/métodos , Ansiedad/psicología , Dolor Crónico/psicología , Depresión/psicología , Síndrome de Fracaso de la Cirugía Espinal Lumbar/patología , Femenino , Humanos , Masculino , Persona de Mediana Edad , Encuestas y Cuestionarios , Resultado del Tratamiento
4.
Transplant Proc ; 48(9): 3227-3230, 2016 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-27932188

RESUMEN

Bone marrow transplantation (BMT) has been performed as a successful life-saving treatment for hematological and neoplastic diseases. Despite the predictable long-term survival rates in BMT, pulmonary complications reduce the survival rates significantly mainly because of chronic graft-versus-host disease (GVHD). This report briefly discusses a successful lung transplantation case for severe lung GVHD after allograft for acute lymphoblastic leukemia. This case report supports the scarce evidence in the literature for the importance of lung transplantation as a therapeutic option for patients who develop respiratory failure secondary to BMT.


Asunto(s)
Trasplante de Médula Ósea/efectos adversos , Enfermedad Injerto contra Huésped/cirugía , Trasplante de Pulmón/métodos , Leucemia-Linfoma Linfoblástico de Células Precursoras/cirugía , Adolescente , Adulto , Aloinjertos , Femenino , Enfermedad Injerto contra Huésped/etiología , Humanos , Masculino , Hermanos , Trasplante Homólogo/efectos adversos
6.
Intern Med J ; 45(12): 1286-92, 2015 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-26348642

RESUMEN

BACKGROUND: Adult allogeneic haemopoietic stem cell transplant (HSCT) usually requires blood transfusion support of red cells and platelets. There are few studies describing transfusion burden after allogeneic HSCT. AIMS: This study aims to quantify and identify determinants of transfusion burden after allogeneic HSCT to improve planning, inventory management and patient counselling. METHODS: A retrospective audit of blood use (red cells and platelets) of all adult HSCT (n = 169) was performed over an 8-year period extracted from pathology and hospital databases. ABO compatibility, graft type, conditioning regimens and patient factors were analysed for up to 12 months post transplant. RESULTS: Transfusion burden was lower than expected and lower than reported by other groups. The median number of units transfused was four red cells and four platelets by day 30, and six red cells and six platelets by day 365. The median time to transfusion independence was 12 days for red cells and 16 days for platelets. Factors associated with increased red cell use included sex, disease stage, graft type (cord blood) and ABO compatibility. Disease stage and graft type (cord blood) were associated with increased platelet transfusion. CONCLUSIONS: Donor and patient characteristics are associated with transfusion burden after allogeneic HSCT. Determining transfusion burden in HSCT and identifying determinants of increased transfusion use assist in inventory planning and patient information.


Asunto(s)
Transfusión de Eritrocitos , Trasplante de Células Madre Hematopoyéticas , Enfermedad de Hodgkin/terapia , Leucemia/terapia , Mieloma Múltiple/terapia , Síndromes Mielodisplásicos/terapia , Transfusión de Plaquetas , Adulto , Consejo Dirigido , Transfusión de Eritrocitos/estadística & datos numéricos , Femenino , Enfermedad Injerto contra Huésped , Trasplante de Células Madre Hematopoyéticas/efectos adversos , Humanos , Masculino , Persona de Mediana Edad , Educación del Paciente como Asunto , Transfusión de Plaquetas/estadística & datos numéricos , Estudios Retrospectivos , Donantes de Tejidos , Acondicionamiento Pretrasplante
7.
Ir J Psychol Med ; 32(3): 265-274, 2015 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-30185265

RESUMEN

OBJECTIVES: Mindfulness-based cognitive therapy (MBCT) is a group-based intervention similar to mindfulness-based stress reduction, but which includes cognitive therapy techniques. This study investigates its usefulness in the treatment of depressive, anxiety and stress/distress symptoms in cancer patients referred to a psycho-oncology service. It also examines whether effect on depression is mediated by self-compassion. METHOD: In phase 1 of this study, 16 cancer patients with mild/moderate psychological distress were randomised to MBCT (n=8) or treatment as usual (TAU; n=8), and assessed pre- and post-treatment. Analysis of variance was performed to examine the effect of treatment on anxiety and depression. In phase 2, the TAU group received the intervention, and results of pre- and post-MBCT assessments were combined with those receiving MBCT in phase 1. Finally, both groups were followed up at 3 months. RESULTS: In phase 1, the MBCT group had a significant improvement in mindfulness and a decrease in anxiety. Statistically significant improvements in both depression and anxiety were found at 3 month follow-up. Self-compassion appeared to mediate the effect on anxiety/depression. CONCLUSION: This small pilot study suggests that MBCT may have a beneficial effect on psychological variables often adversely affected in cancer in a heterogeneous cancer population.

8.
Ir J Psychol Med ; 31(3): 191-193, 2014 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-30189491

RESUMEN

BACKGROUND: Co-prescription of linezolid and serotonergic agents (SSRIs, SNRIs, NaSSA, TCAs) can lead to serotonin syndrome, this study seeks to identify prescribing practise of these agents. METHODS: Study of all general hospital inpatients prescribed intravenous linezolid in a 3-month period, using drug charts and clinical notes. RESULTS: Co-prescription occurred in 20% with SSRIs most frequently concurrently used. There were no cases of serotonin syndrome. There was no evidence in clinical notes of vigilance for potential interaction. CONCLUSION: Co-prescription is common; awareness of potentially serious interaction is not evident in current practice.

9.
Food Microbiol ; 32(2): 354-60, 2012 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-22986201

RESUMEN

Two bacterial isolates with inhibitory activity against Listeria monocytogenes and Enterococcus faecalis were obtained from soil. Genotypic and phenotypic characterization identified them as Enterococcus mundtii, a species whose ability to compete with L. monocytogenes is relatively unexplored compared to other members of the genus. The thermal stability of the inhibitory factor and its sensitivity to proteolytic enzymes indicate that it is most likely a bacteriocin. Both isolates grew at comparable rates to L. monocytogenes at 5 °C and 10 °C in vitro. One isolate killed L. monocytogenes when it reached concentrations of 10(6)-10(8) CFU ml(-1). Minimum inocula of 10(6) and 10(5) CFU ml(-1) of E. mundtii were required to reduce and maintain L. monocytogenes concentrations beneath the level of detection at 5 °C and 10 °C, respectively. In situ experiments at 5 °C showed that E. mundtii inhibited the growth of L. monocytogenes on vacuum-packed cold smoked salmon during its four week shelf life. E. mundtii could, therefore, control the growth of L. monocytogenes at low temperatures, indicating a potential application in controlling this pathogen in chilled foods. To control growth of Listeria, the concentration of E. mundtii needs to be high, but it is possible that a purified bacteriocin could be used to achieve the same effect.


Asunto(s)
Bacteriocinas/metabolismo , Enterococcus faecalis/crecimiento & desarrollo , Enterococcus/aislamiento & purificación , Enterococcus/metabolismo , Listeria monocytogenes/crecimiento & desarrollo , Microbiología del Suelo , Animales , Bacteriocinas/farmacología , Enterococcus/química , Enterococcus/genética , Enterococcus faecalis/efectos de los fármacos , Conservación de Alimentos , Listeria monocytogenes/efectos de los fármacos , Salmón/microbiología , Alimentos Marinos/microbiología
10.
Intern Med J ; 42(9): 1008-13, 2012 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-21981267

RESUMEN

BACKGROUND/AIMS: Thirty-one umbilical cord blood transplants performed in Western Australia were retrospectively examined in order to document local experience and relevant prognostic factors. Three cord units were from human leucocyte antigen-matched siblings and the remainder were unrelated single (n= 22) or double (n= 6) cord blood transplants. METHODS: Twenty patients were transplanted for malignant conditions and 11 for non-malignant conditions. Cord units contained a median of 5.6 × 107 total nucleated cells/kg and 1.4 × 105 CD34+ cells/kg. Cumulative incidence of neutrophil engraftment was 76% at day 60. RESULTS: Of those who did not engraft, two patients remain alive following subsequent allogeneic bone marrow transplant. There were no deaths caused by graft-versus-host disease. Overall survival at median follow up of 28 months was 62%. Two year overall survival was influenced by type of disease (non-malignant = 91 ± 9% vs malignant = 41 ± 13%, P= 0.005), total nucleated cell dose (>3.5 × 107/kg = 87 ± 9% vs <3.5 × 107/kg = 34 ± 15%, P= 0.01) and CD34 dose (>1.7 × 105/kg = 92% vs <1.7 × 105/kg = 46%, P= 0.04). Age and human leucocyte antigen match did not influence survival. Four relapses occurred, all of which were fatal. CONCLUSION: Cord blood transplantation for malignant and non-malignant disease is practised in Western Australia and outcomes are satisfactory. Trends and techniques in cord blood transplantation in this state are comparable with those observed nationally and overseas. Although numbers are small, cell dose appears to be predictive of overall survival


Asunto(s)
Trasplante de Células Madre de Sangre del Cordón Umbilical/estadística & datos numéricos , Adolescente , Adulto , Anciano de 80 o más Años , Aloinjertos , Trasplante de Médula Ósea/estadística & datos numéricos , Niño , Preescolar , Trasplante de Células Madre de Sangre del Cordón Umbilical/mortalidad , Trasplante de Células Madre de Sangre del Cordón Umbilical/tendencias , Femenino , Enfermedades Genéticas Congénitas/cirugía , Supervivencia de Injerto , Enfermedad Injerto contra Huésped/epidemiología , Neoplasias Hematológicas/cirugía , Prueba de Histocompatibilidad , Humanos , Terapia de Inmunosupresión , Lactante , Masculino , Persona de Mediana Edad , Recurrencia , Estudios Retrospectivos , Tasa de Supervivencia , Australia Occidental , Adulto Joven
11.
Intern Med J ; 41(8): 588-94, 2011 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-21831119

RESUMEN

Mobilization and collection of haemopoietic stem and progenitor cells (HSPC) is the cornerstone of autologous and allogeneic stem cell transplantation for a wide variety of haematological and some non-haematological malignancies. Centres providing this service face the challenge of optimizing the likelihood of successful collection of transplantable doses of cells, while maximizing the efficiency of the apheresis unit and minimizing the risk of toxicity as well as mobilization failure. Recent developments in the understanding of the molecular mechanisms of mobilization have led to the emergence of novel strategies for HSPC mobilization, which may assist in meeting these imperatives. The task for clinicians is how to incorporate the use of these strategies into practice, in the light of emerging evidence for efficacy and safety of these agents. Herein, the literature is reviewed, and a proposed algorithm for HSPC mobilization is presented.


Asunto(s)
Movilización de Célula Madre Hematopoyética/métodos , Trasplante de Células Madre Hematopoyéticas/métodos , Células Madre Hematopoyéticas/fisiología , Animales , Eliminación de Componentes Sanguíneos/métodos , Eliminación de Componentes Sanguíneos/normas , Células de la Médula Ósea/fisiología , Factor Estimulante de Colonias de Granulocitos/administración & dosificación , Movilización de Célula Madre Hematopoyética/normas , Trasplante de Células Madre Hematopoyéticas/normas , Células Madre Hematopoyéticas/citología , Humanos
12.
Intern Med J ; 41(1b): 82-9, 2011 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-21272172

RESUMEN

Utilization of risk-stratification tools in the setting of neutropenic fever is currently limited by inadequate knowledge and lack of awareness. Within this context, the approach to management of low-risk patients with neutropenic fever is inconsistent with the available evidence across many Australian treating centres. These clinical guidelines define and clarify an accepted standard of care for this patient group given the current evidence base. The Multinational Association for Supportive Care in Cancer risk index is presented as the preferred risk assessment tool for determining patient risk. Suitability of ambulatory care within specific patient populations is discussed, with defined eligibility criteria provided to guide clinical decision-making. Detailed recommendations for implementing appropriate ambulatory strategies, such as early discharge and outpatient antibiotic therapy, are also provided. Due consideration is given to infrastructural requirements and other supportive measures at a resourcing and operational level. An analysis of the relevant health economics is also presented.


Asunto(s)
Atención Ambulatoria/métodos , Manejo de la Enfermedad , Fiebre/tratamiento farmacológico , Neoplasias/complicaciones , Neutropenia/complicaciones , Gestión de Riesgos , Índice de Severidad de la Enfermedad , Adulto , Atención Ambulatoria/organización & administración , Antibacterianos/uso terapéutico , Australia , Instituciones Oncológicas/organización & administración , Instituciones Oncológicas/normas , Farmacorresistencia Bacteriana Múltiple , Medicina Basada en la Evidencia , Fiebre/etiología , Humanos , Grupo de Atención al Paciente , Alta del Paciente , Pautas de la Práctica en Medicina , Recurrencia , Riesgo
14.
Am J Physiol Regul Integr Comp Physiol ; 297(1): R70-81, 2009 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-19403859

RESUMEN

Exercise-induced oxidative stress is instrumental in achieving the health benefits from regular exercise. Therefore, inappropriate use of fruit-derived products (commonly applied as prophalytic antioxidants) may counteract the positive effects of exercise. Using human exercise and cellular models we found that 1) blackcurrant supplementation suppressed exercise-induced oxidative stress, e.g., plasma carbonyls (0.9 +/- 0.1 vs. 0.6 +/- 0.1 nmol/mg protein, placebo vs. blackcurrant), and 2) preincubation of THP-1 cells with an anthocyanin-rich blackcurrant extract inhibited LPS-stimulated cytokine secretion [TNF-alpha (16,453 +/- 322 vs. 10,941 +/- 82 pg/ml, control vs. extract, P < 0.05) and IL-6 (476 +/- 14 vs. 326 +/- 32 pg/ml, control vs. extract, P < 0.05)] and NF-kappaB activation. In addition to its antioxidant and anti-inflammatory properties, we found that postexercise plasma collected after blackcurrant supplementation enhanced the differential temporal LPS-stimulated inflammatory response in THP-1 cells, resulting in an early suppression of TNF-alpha (1,741 +/- 32 vs. 1,312 +/- 42 pg/ml, placebo vs. blackcurrant, P < 0.05) and IL-6 (44 +/- 5 vs. 36 +/- 3 pg/ml, placebo vs. blackcurrant, P < 0.05) secretion after 24 h. Furthermore, by using an oxidative stress cell model, we found that preincubation of THP-1 cells with hydrogen peroxide (H(2)O(2)) prior to extract exposure caused a greater suppression of LPS-stimulated cytokine secretion after 24 h, which was not evident when cells were simultaneously incubated with H(2)O(2) and the extract. In summary, our findings support the concept that consumption of blackcurrant anthocyanins alleviate oxidative stress, and may, if given at the appropriate amount and time, complement the ability of exercise to enhance immune responsiveness to potential pathogens.


Asunto(s)
Antocianinas/administración & dosificación , Antiinflamatorios/administración & dosificación , Antioxidantes/administración & dosificación , Suplementos Dietéticos , Ejercicio Físico , Inflamación/prevención & control , Estrés Oxidativo/efectos de los fármacos , Ribes , Adulto , Antocianinas/aislamiento & purificación , Antiinflamatorios/aislamiento & purificación , Antioxidantes/aislamiento & purificación , Línea Celular , Estudios Cruzados , Relación Dosis-Respuesta a Droga , Método Doble Ciego , Esquema de Medicación , Femenino , Frutas , Humanos , Proteínas I-kappa B/metabolismo , Inflamación/inmunología , Interleucina-6/sangre , Lipopolisacáridos , Masculino , Persona de Mediana Edad , Monocitos/efectos de los fármacos , Monocitos/inmunología , Inhibidor NF-kappaB alfa , Extractos Vegetales/administración & dosificación , Carbonilación Proteica/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismo , Ribes/química , Factores de Tiempo , Factor de Transcripción ReIA/metabolismo , Factor de Necrosis Tumoral alfa/sangre
15.
J Biomed Mater Res B Appl Biomater ; 90(2): 700-9, 2009 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-19213053

RESUMEN

Primary deep infection following joint replacement surgery accounts for 7% of all revisions. Glass polyalkenoate cements (GPCs) have previously been shown to exhibit antibacterial properties. The present study had two objectives. The first was to determine if addition of tri-sodium citrate (TSC) to the powder phase of an Al-free GPC (0.04 SrO-0.12 CaO-0.36 ZnO-0.48 SiO2, by mole fraction) enhanced the resultant cement's antibacterial properties against three strains of bacteria that are commonly found in periprosthetic sites following total joint replacements (TJRs); namely, E. coli, B. fragilis, and S. epidermidis. Four cement sets were prepared, which contained 0 wt% TSC (control), 5 wt% TSC, 10 wt% TSC, and 15 wt% TSC. All the TSC-modified cements were found to exhibit large inhibition zones against all the bacterial strains, especially the cement containing 15 wt% TSC against E. coli. The antibacterial properties of the TSC containing GPCs are attributed to the release of Zn and Na ions from the cements and the presence of the TSC. The second objective was to investigate if, when a modified GPC is embedded in a bovine bone model, ionic transfer occurs. It was found that Zn ions migrated from the cement to the surrounding bone, particularly at the cement-bone interface. This is a desirable outcome as Zn ions are known to play a vital role in both bone metabolism and the regeneration of healthy bone. The present results point to the potential clinical benefits of using TSC-modified GPCs in TJRs.


Asunto(s)
Antibacterianos/farmacología , Cementos para Huesos/química , Citratos/farmacología , Cementos de Ionómero Vítreo/química , Animales , Antiinfecciosos/farmacología , Huesos/metabolismo , Bovinos , Citratos/química , Vidrio , Iones , Pruebas de Sensibilidad Microbiana , Silicatos/química , Dióxido de Silicio/química , Sodio/química , Estroncio/química , Zinc/química
16.
Inorg Chem ; 46(25): 10639-46, 2007 Dec 10.
Artículo en Inglés | MEDLINE | ID: mdl-18001112

RESUMEN

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal center. Comparison with previously studied Cp2M(dithiolate) complexes, where M is Ti and Mo (respectively d0 and d2 electron configurations), allows evaluation of d0, d1, and d2 electronic configurations of the metal center that are analogues for the metal oxidation states present throughout the catalytic cycle of these enzymes. A "dithiolate-folding effect" that involves an interaction between the vanadium d orbitals and sulfur p orbitals is shown to stabilize the d1 metal center, allowing the d1 electron configuration and geometry to act as a low-energy electron pathway intermediate between the d0 and d2 electron configurations of the enzyme.


Asunto(s)
Quelantes/química , Electrones , Molibdeno/química , Pterinas/química , Compuestos de Sulfhidrilo/química , Tungsteno/química , Compuestos de Vanadio/química , Cristalografía por Rayos X , Iones/química , Ligandos , Modelos Moleculares , Conformación Molecular , Estructura Molecular , Fotoquímica , Espectrofotometría , Temperatura
17.
J Am Chem Soc ; 127(47): 16713-22, 2005 Nov 30.
Artículo en Inglés | MEDLINE | ID: mdl-16305262

RESUMEN

Ka band ESEEM spectroscopy was used to determine the hyperfine (hfi) and nuclear quadrupole (nqi) interaction parameters for the oxo-17O ligand in [Mo 17O(SPh)4]-, a spectroscopic model of the oxo-Mo(V) centers of enzymes. The isotropic hfi constant of 6.5 MHz found for the oxo-17O is much smaller than the values of approximately 20-40 MHz typical for the 17O nucleus of an equatorial OH(2) ligand in molybdenum enzymes. The 17O nqi parameter (e2qQ/h = 1.45 MHz, eta approximately = 0) is the first to be obtained for an oxo group in a metal complex. The parameters of the oxo-17O ligand, as well as other magnetic resonance parameters of [Mo 17O(SPh)4]- predicted by quasi-relativistic DFT calculations, were in good agreement with those obtained in experiment. From the electronic structure of the complex revealed by DFT, it follows that the SOMO is almost entirely molybdenum d(xy) and sulfur p, while the spin density on the oxo-17O is negative, determined by spin polarization mechanisms. The results of this work will enable direct experimental identification of the oxo ligand in a variety of chemical and biological systems.


Asunto(s)
Enzimas/química , Modelos Moleculares , Molibdeno/química , Espectroscopía de Resonancia por Spin del Electrón , Enzimas/metabolismo , Metaloproteasas/química , Metaloproteasas/metabolismo , Molibdeno/metabolismo , Isótopos de Oxígeno
18.
Br J Anaesth ; 95(1): 112-3, 2005 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-15941738
19.
Inorg Chem ; 43(25): 8110-8, 2004 Dec 13.
Artículo en Inglés | MEDLINE | ID: mdl-15578851

RESUMEN

Gas-phase photoelectron spectroscopy and density functional theory have been utilized to investigate the interactions between the p orbitals of dithiolate ligands and d orbitals of titanium in bent titanocene complexes as minimum molecular models of active site features of pyranopterin Mo/W enzymes. The compounds Cp(2)Ti(S-S) [where (S-S) is 1,2-ethenedithiolate (S(2)C(2)H(2)), 1, 1,2-benzenedithiolate (bdt), 2, or 1,3-propanedithiolate (pdt), 3, and Cp(-) is cyclopentadienyl] provide access to a formal 16-electron d(0) electronic configuration at the metal. A "dithiolate-folding-effect" involving an interaction of metal and sulfur orbitals is demonstrated in complexes with arene- and enedithiolates. This effect is not observed for the alkanedithiolate in complex 3.


Asunto(s)
Molibdeno/química , Compuestos Organometálicos/química , Oxidorreductasas actuantes sobre Donantes de Grupos Sulfuro/química , Compuestos de Sulfhidrilo/química , Sitios de Unión , Electroquímica , Cinética , Ligandos , Modelos Moleculares , Conformación Molecular , Molibdeno/metabolismo , Compuestos Organometálicos/metabolismo , Compuestos de Sulfhidrilo/metabolismo
20.
Inorg Chem ; 43(15): 4532-3, 2004 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-15257571

RESUMEN

Synthesis of [PPh4]2[Mo(SPh)2(S2C2(CN)2)2] (2) from [PPh4]2[MoO(S2C2(CN)2)2] (1) has been achieved to mimic the postulated [Mo(S)6] core of polysulfide reductase with two thiolates and two bis(ene-dithiolate) ligands. Compound 2 reacts with polysulfide to yield H2S, modeling the function of polysulfide reductase. The facile conversion of 2 back to 1 in moist solvent suggests that the interconversion of the [MoIV = O] and [MoIV - X] (X = O-Ser, S-Cys, Se-Cys) moieties might occur in the DMSO reductase class of enzymes under appropriate hydrophobic/hydrophilic conditions.


Asunto(s)
Molibdeno/química , Compuestos Organometálicos/química , Compuestos Organometálicos/síntesis química , Oxidorreductasas/química , Oxidorreductasas/metabolismo , Wolinella/enzimología , Sitios de Unión , Cristalografía por Rayos X , Cisteína/química , Cisteína/metabolismo , Modelos Moleculares , Conformación Molecular , Estructura Molecular , Compuestos Organometálicos/metabolismo
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